Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• This invention relates to polymers comprising carbonyl groups in their backbone, such as polyesters and polyimides, which have been modified by compounds having ketonic groups in their backbone.
• these compounds Preferably, these compounds have also ether groups in their backbone.
• a number of polymers which contain carbonyl groups in their backbones such as for example polyesters and polyimides, depending on their structure, may be hard, stiff, and difficult to process. However, they are valuable because of other desirable properties, which vary depending on the application.
• Polyesters are usually less expensive than polyimides, and they may be preferred to polyimides for this reason in a number of occasions, if the requirements for the particular application permit; for example, if the end-use temperature is not very high.
• Polyimides constitute a class of valuable polymers being characterized by thermal stability, inert character, usual insolubility in even strong solvents, and high T g , among others. Their precursors are usually polyamic acids, which may take the final imidized form either by thermal or by chemical treatment. Polyimides have always found a large number of applications requiring the aforementioned characteristics in numerous industries, and recently their applications have started increasing dramatically in electronic devices, especially as dielectrics. With continuously escalating sophistication in such devices, the demands on the properties and the property control are becoming rather vexatious.
• polyethers and polyetherketones of at least moderate average molecular weight have been utilized in the past, admixed with the polyesters and the polyimides under consideration for lowering the T g .
• plasticizers with other polymers are avoided in this case as subject to exudation sooner or later, and other disadvantages, such as for example lack of high thermal stability, volatility at high processing temperatures, and the like.
• thermoplastic polymer composition comprising in admixture, a thermoplastic polymer selected from a polyarylate, a polyetherimide, an aromatic polycarbonate, a poly(aryl ether) having a molecular weight in excess of 10,000 and mixtures thereof and a plasticizing amount of a poly(aryl ether) having a molecular weight of from about 1,000 to about 5,000.
• thermoplastic, injection moldable composites comprising at least one poly(aryl ether ketone) having silicon carbide whiskers dispersed therein exhibit excellent tensile properties coupled with high elongation relative to poly(aryl ether ketone) composites with other inorganic fibers.
• the composites are useful for making articles such as electrical connectors.
• U.S. Pat. No. 4,703,081 (Blackwell et al.), issued Oct. 27, 1987, describes a ternary polymer alloy containing a poly(arylene sulfide), a poly(amide imide), and at least one of a poly(aryl ketone) and a poly(aryl sulfone).
• the polymer alloy optionally can contain a fibrous reinforcing material such as a glass fiber.
• European Patent Application Publication 0 167 897 A1 (Dickinson), published Jan. 15, 1986, is directed to a plasticized polyarylate composition
• a plasticized polyarylate composition comprising in admixture, a polyarylate, derived from a dihydric phenol and at least one aromatic dicarboxylic acid and having a reduced viscosity of from about 0.4 to greater than 1. dc/g, from about 5 to 30 weight percent of glass fibers, and a plasticizing amount of an oligomeric poly(aryl) ether having a reduced viscosity of from about 0.1 to about 0.45 dl/g.
• the present invention utilizes ketone and etherketone compounds as opposed to polymers or oligomers, which have molecular weights in a specific range between about 300 and under 1,000.
• Compounds are substantially monodisperse moieties, while polymers or oligomers have typically a large polydispersity, unless specific procedures have been used in their preparation. Even then, only in limited situations it is possible to reach a polydispersity lower than 2.
• the compatibility of higher molecular weight polymers, especially in the case of some polyesters is better with lower molecular weight moieties.
• compositions where the modifier is a ketonic compound, preferably containing ether groups in the backbone, and having a molecular weight in the region of 300 to under 1,000.
• the references recognizes the importance of utilizing in the composition substantially monodisperse modifiers.
• the instant invention is directed to polymers comprising carbonyl groups in their backbone, such as polyesters and polyimides, which have been modified by compounds having ketonic groups in their backbone, and molecular weights in the region of 300 to under 1,000.
• these compounds Preferably, these compounds have also ether groups in their backbone.
• this invention pertains to a composition of matter comprising:
• condensation polymer selected from the group consisting of polyester and polyimide
• composition of matter comprising:
• condensation polymer selected from the group consisting of polyester and polyimide
• a modifier consisting essentially of a compound having a formula ##STR2##
• the modifier in both cases has a polydispersity of substantially 1.
• the instant invention is directed to polymers comprising carbonyl groups in their backbone, such as polyesters and polyimides, which have been modified by compounds, as opposed to polymers, having ketonic groups in their backbone, and molecular weights in the region of 300 to under 1,000.
• these compounds have also ether groups in their backbone.
• polyesters and polyimides utilized in the practice of the present invention may be prepared in any number of conventional ways well known to the art. Depending on their structure and on the function that they have to fulfill, however, they may be too hard, or too stiff, or too difficult to process thermally, and the like. Nevertheless, many times they are valuable because of other desirable properties, which vary, depending on the final application.
• polyethers and polyetherketones of at least moderate weight average molecular weight in the form of oligomers or polymers have been utilized, admixed with the polyesters and the polyimides under consideration for lowering the T g .
• the compounds of the present invention have molecular weights in the range of 300-1000, they are adequately non-volatile to substantially avoid evaporation during curing or processing of the polymer which they modify, and at the same time their effect, especially regarding T g and melt viscosity, is maximized.
• the level of modifier that can be incorporated into a polyimide or polyester may be determined partially by the miscibility characteristics of the compound with the structure of the polymer.
• polyester materials it is expected that many structures are miscible with the modifiers, while others, especially those of the liquid crystal polymer (LCP) variety, may be immiscible or display a miscibility limit based on structure. In that case, a point is reached where the compound no longer forms a homogeneous blend and phase-separates from the polymer. Such a situation is normally undesirable from a property standpoint, so that exceeding this limit should typically be avoided.
• polyimide and polyetherimide structures are also expected to be miscible with the modifying compounds; however, some structures, especially those of very rigid nature, e.g., BPDA/PPD or PMDA/PPD) may be expected to have a lower miscibility limit or be immiscible.
• the level at which a miscibility limit occurs is governed to some extent by the molecular weight of the modifier. Generally, the higher the molecular weight, the lower the miscibility limit in the polymer. On the other hand, while a lower molecular weight additive tends to have a larger impact on properties and better miscibility, a lower limit of molecular weight is reached, beyond which the volatility of the modifier is undesirably high at polymer processing temperatures.
• the level of modifier that can be incorporated may also be limited by the amount that can be used while maintaining desired mechanical property levels, since low molecular weight compounds would be typically be expected to deteriorate the mechanical properties of polymers when used in excessive amounts.
• polyimides may be prepared which exhibit crystalline transition(s) as-prepared, but lose this crystallinity once heated or processed about the transition temperature. Normally, this crystallinity is not recoverable. Since it is known that crystallinity in polymers often leads to useful property improvements, e.g., strength, modulus, solvent resistance, it is desirable to develop methods whereby crystallinity in polyimides may be achieved or enhanced. Such methods in which the solvent N-methyl-2-pyrrolidone is used to treat amorphous samples of a polyimide known commonly as LARC-TPI are known to the artisans. Although this method has been shown to induce crystallinity in LARC-TPI, generally solvent treatment after processing to induce crystallinity in prepared parts is undesirable from a commercial standpoint.
• the compounds of the present invention fulfill such a need in that it has been demonstrated that crystallinity may be achieved during melt processing of a polyimide such that a semicrystalline polyimide may be achieved directly from extrusion or injection molding.
• the compounds of the present invention have the advantage over solvents in that their higher molecular weight and low volatility minimizes their loss via outgassing during high temperature processing and the shrinkage and voiding that might accompany such loss.
• Table 1 summarizes the performance of modifier in polyimides. It is very important to note that even small amounts, in the region of 5-10% by weight, decrease the water absorption considerably. Also in the Examples, it is shown that the melt viscosity and T g decrease appreciably with relatively small amounts of modifier.
• the crystallization of polyimides may also be enabled or enhanced by the presence of the modifying compounds of the present invention. Often, the more crystalline a polymer the better its functional properties, such as for example solvent resistance, heat resistance, and the like. This is a very high attribute that the modifiers of the present invention offer.
• a soluble modifier may be required, such as in the case where, the polyimide for example is to be applied on a substrate as a coating from solvent at room temperature.
• DID 1,3-bis(4-phenoxybenzoyl)benzene
• DTD 1,4-bis(4-phenoxybenzoyl)benzene
• polymers of the polyether ketone type are typically either insoluble, or have reduced solubility, or may increase solution viscosity in solution coatings, such that they are typically unsuitable for addition to poly(amic acid) solutions. This is one of the reasons why polyether ketones or oligomeric ether ketones are not as good as compounds of this invention.
• compositions of the present invention comprise a condensation polymer selected from the group consisting of polyesters and polyimides, having a weight average molecular weight higher than 10,000. It is important that the weight average molecular weight is preferably higher than 15,000, more preferably higher than 20,000, and even more preferably in the range of 30,000 to 300,000, so that it provides the polymer with generally good functional properties.
• the modifier compounds utilized according to the present invention may be made so that they have a polydispersity of substantially 1, in contrast to polymeric species containing a larger number of the same or similar units, which develop polydispersities differing considerably from 1.
• compositions made by adding modifiers similar to those of the present invention in the form of low molecular weight tail of a polymeric species having high polydispersity are certainly inferior when compared to compositions made by adding the modifier of this invention in its substantially monodisperse form.
• the major active ingredient constitutes only a small amount of the total additive, while in the latter case it constitutes substantially 100% of the major active ingredient.
• the inactive ingredient is undesirable as an ingredient of the polyimide or polyester as it may deteriorate their properties, including reproducibility and solubility.
• R 1 is ##STR4## and R 2 is
• R 0 is preferably ##STR5##
• R 1 is ##STR6## and R 2 is ##STR7## while R 0 is preferably ##STR8##
• the modifier is ##STR9## Examples demonstrating the instant invention are given below for illustration purposes only, and should not be construed as restricting the scope or limits of this invention in any way. All parts and percents are by weight and degrees are in centigrade unless otherwise indicated.
• Avimid K Polyimide based on pyromellitic dianhydride from Du Pont, Wilmington, Del.
• BDTDB 1,4-bis ⁇ 4-([4-benzoyl]phenoxy)benzoyl ⁇ benzene
• J/g Joules per gram
• Pyralin® PI-2611 BPDA/PPD poly(amic acid) solution from Du Pont, Wilmington, Del.
• DTD 1,4-bis(4-phenoxybenzoyl)benzene
• Example 2 A similar procedure as that given in Example 1 was followed except that 63 g of Avimid K polyimide powder was blended with 7 g of 1,4-bis(4-phenoxybenzoyl)benzene (DTD) (90% Avimid K, 10% DTD). The blend exhibited a T g of 216° C. and a melt viscosity of 670 Pa.s at 385 1/s.
• DTD 1,4-bis(4-phenoxybenzoyl)benzene
• DTD 1,4-bis(4-phenoxybenzoyl)benzene
• DTD 1,4-bis(4-phenoxybenzoyl)benzene
• Example 4 A procedure similar to that given in Example 4 was used to prepare another 80/20 ⁇ Avimid K ⁇ / ⁇ 1,4-bis(4-phenoxybenzoyl)benzene ⁇ blend. This blend was melted and ram press spun through a spinneret (3380 micron diameter holes, 1.14 l/d ratio, stainless steel mesh screens in order of distance from spinneret of 50-325-50-200-50-100-50 mesh), at 352° C. spinneret temperature and 1570 psi ram pressure, and wound up at 386 to 950 meters/min to produce tough, lustrous monofilament fibers which at a windup speed of 650 meters/min had the following tensile properties:
• Example 9 A similar procedure to that given in Example 9 was followed except that the spin coated poly(amic acid) films were heated at 135° C. for 30 minutes and then at 300° C. for 1 hour to obtain the polyimide film.
• Property data are included in Table 1.
• Example 11 A similar procedure to that given in Example 11 was followed except that the spin coated poly(amic acid) films were heated at 135° C. for 30 minutes and then at 300° C. for 1 hour to obtain the polyimide film.
• Property data are included in Table 1.
• Example 13 A similar procedure to that given in Example 13 was followed except that the spin coated poly(amic acid) films were heated at 135° C. for 30 minutes and then at 300° C. for 1 hour to obtain the polyimide film.
• Property data ar included in Table 1.
• a commerical poly(amic acid) solution Du Pont Pyralin® PI-2611
• DID 1,3-bis(4-phenoxybenzoyl)benzene
• Example 15 A similar procedure to that given in Example 15 was followed except that the spin coated poly(amic acid) films were heated at 135° C. for 30 minutes and then at 300° C. for 1 hour to obtain the polyimide film.
• Property data are included in Table 1.
• LCP amorphous Du Pont Liquid Crystal Polymer
• HX-2000 aromatic liquid crystalline polyester
• ODBP oxydibenzophenone
• the polymer melt was removed from the mixer via a brass spatula, allowed to cool to room temperature and then ground to a coarse powder in a Thomas cutter. The same procedure was followed to prepare a control sample containing no modifier.
• DSC measurements Du Pont 1090, 20° C./min, 2nd heating scan
• Gel permeation chromatography of the Liquid Crystal Polymer (LCP) samples containing the modifiers revealed essentially no degradation of the polymer molecular weight by these modifiers.
• LCP Du Pont Liquid Crystal Polymer
• HX-3000 aromatic liquid crystalline polyester
• DTD 1,4ibis(4-phenoxybenzoyl)benzene
• Harbison Walker GP7I Harbison Walker GP7I fused silica
• the polymer melt was removed from the mixer via a brass spatula, allowed to cool to room temperature and then ground to a coarse powder in a Thomas cutter.
• the same procedure was followed to prepare a similar compound containing only Liquid Crystal Polymer (LCP) and silica but no 1,4-bis(4-phenoxybenzoyl)benzene (DTD) (48 g LCP, 72 g silica, control sample).
• DSC measurements Du Pont 1090, 20° C./min, 2nd heating scan
• Example 13 A similar polyester (56 g) to that described in Example 13 was dry blended with 14 g of oxydibenzophenone (ODBP) (20 wt. % ODBP). By the same procedure as that described in Example 13, this blend exhibited a T g of 104° C. vs. that of the same material without oxydibenzophenone (ODBP) which gave a T g of 181° C. again indicating the plasticizing ability of the modifier.
• ODBP oxydibenzophenone
• the solution was very slowly poured into agitated chilled demineralized water to deactivate the aluminum chloride (maximum water temperature reached was 28° C.). After stirring for 10 minutes, stirring was stopped and the very acidic upper layer was decanted off. The organic layer was subsequently washed several times with fresh dimeneralized water to remove the acid and filtered to remove solid impurities, e.g., elemental aluminum). Afterwards, methanol was slowly added to the organic layer (about 1/1 on a volume basis) with stirring and the product precipitated as short, white needles. Further purification was undertaken by slurrying 3X in isopropanol followed by filtration and drying. The short needles gave a DSC melting point (20° C./min) of 124° C.
• Example 23 A similar procedure to Example 23 is followed, except o-dichlorobenzene is used as reaction solvent.
• the product is isolated by deactivating the aluminum chloride with water.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyethers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polyesters Or Polycarbonates (AREA)
• Phenolic Resins Or Amino Resins (AREA)

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